Flame retardant resin compositions containing phosphoramides, and method of making

ABSTRACT

The present invention provides resin compositions comprising a thermoplastic resin, at least one phosphoramide having a glass transition point of at least about 0° C. preferably of at least about 10° C., and most preferably of at least about 20° C.; and at least one adjunct flame retardant. The present invention also relates to articles made from the resin compositions. The present invention also provides methods to make the resin compositions having improved heat properties over compositions known in the art.

This application is a continuation-in-part of application Ser. No.09/404,459, filed Jul. 8, 1999, now U.S. Pat. No. 6,228,912, which is acontinuation-in-part of application Ser. No. 09/235,680, filed Jan. 22,1999, now abandoned, which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to resin compositions comprising aphosphoramide compound having a glass transition temperature of at leastabout 0° C., preferably of at least about 10° C., and most preferably ofat least about 20° C. The invention also relates to methods to make theresin compositions and articles made from the resin compositions.

Compounds containing phosphorus have been used in resin compositions fora variety of reasons. For example, various phosphites have been utilizedto enhance the melt stability and/or color stability of resincompositions. Alternatively, various organic phosphate esters have beenutilized in resin compositions to improve the flame resistanceproperties of the compositions and/or to enhance the melt flowcharacteristics of the compositions. Certain water solublephosphoramides have also been used in the textile industry as flameretardant finishes for fabrics.

As part consolidation and weight reduction continues to evolve in manyindustries, the physical property demands placed upon resinmanufacturers are increasing. Key industries increasing the demandsinclude the electronics and computer industries, especially for computerhousings, computer monitor housings, and printer housings. Oneincreasing demand is for materials that possess higher heat resistancewhile preferably substantially retaining other key physical properties.Another increasing demand is for materials that are rated in theUnderwriter's Laboratory UL-94 test protocol as V-0, V-1, or V-2. It istherefore apparent that new resin compositions that meet these and otherdemands continue to be sought.

SUMMARY OF THE INVENTION

The present invention provides flame retardant resin compositionscomprising the following and any reaction products thereof:

a) at least one thermoplastic resin;

b) at least one phosphoramide having a glass transition point of atleast about 0° C., preferably of at least about 10° C., and mostpreferably of at least about 20° C., of the formula:

wherein Q¹ is oxygen or sulfur; R¹ is an amine residue, and R² and R³are each independently an alkyloxy, alkylthio, aryloxy, or arylthioresidue, or an aryloxy or arylthio residue containing at least one alkylsubstitution; or an amine residue; and

c) at least one adjunct flame retardant compound.

The present invention also provides articles made from the resincompositions. Furthermore, the present invention provides methods tomake resin compositions having improved heat and/or processability overcompositions known in the art.

DETAILED DESCRIPTION OF THE INVENTION

The major constituent of the compositions of the invention is at leastone thermoplastic polymer. Both addition and condensation polymers areincluded. Illustrative, non-limiting examples of thermoplastic polymersare olefin polymers such as polyethylene and polypropylene; dienepolymers such as polybutadiene and polyisoprene; polymers ofethylenically unsaturated carboxylic acids and their functionalderivatives, including acrylic polymers such as poly(alkyl acrylates),poly(alkyl methacrylates), polyacrylamides, polyacrylonitrile andpolyacrylic acid; alkenylaromatic polymers such as polystyrene,poly-alpha-methylstyrene, polyvinyltoluene, rubber-modifiedpolystyreries, and the like; polyamides such as nylon-6 and nylon-66;polyesters; polycarbonates; and polyarylene ethers.

Both thermoplastic and thermoplastic elastomeric polyesters are suitablefor use in the present invention. Illustrative, non-limiting examples ofthermoplastic polyesters include poly(ethylene terephthalate),poly(1,4-butylene terephthalate), poly(1,3-propylene terephthalate),polycyclohexanedimethanol terephthalate,polycyclohexanedimethanol-co-ethylene terephthalate, polyethylenenaphthalate, polybutylene naphthalate, and polyarylates. Illustrative,non-limiting examples of thermoplastic elastomeric polyesters (commonlyknown as TPE) include polyetheresters such as poly(alkyleneterephthalate)s (particularly poly[ethylene terephthalate] andpoly[butylene terephthalate]) containing soft-block segments ofpoly(alkylene oxide), particularly segments of poly(ethylene oxide) andpoly(butylene oxide); and polyesteramides such as those synthesized bythe condensation of an aromatic diisocyanate with dicarboxylic acids anda carboxylic acid-terminated polyester or polyether prepolymer.

Suitable polyarylates include, but are not limited to, the polyphthalateesters of 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenolA), and polyesters consisting of structural units of the formula II:

wherein R⁴ is hydrogen or C₁₋₄ alkyl, optionally in combination withstructural units of the formula III:

wherein R₅ is a divalent C₄₋₁₂ aliphatic, alicyclic or mixedaliphatic-alicyclic radical. The latter polyesters are prepared by thereaction of a 1,3-dihydroxy-benzene with at least one aromaticdicarboxylic acid chloride under alkaline conditions. Structural unitsof formula II contain a 1,3-dihydroxybenzene moiety which may besubstituted with halogen, usually chlorine or bromine, or preferablywith C₁₋₄ alkyl; e.g., methyl, ethyl, isopropyl, propyl, butyl. Saidalkyl groups are preferably primary or secondary groups, with methylbeing more preferred, and are most often located in the ortho positionto both oxygen atoms although other positions are also contemplated. Themost preferred moieties are resorcinol moieties, in which R⁴ ishydrogen. Said 1,3-dihydroxybenzene moieties are linked to aromaticdicarboxylic acid moieties which may be monocyclic moieties, e.g.,isophthalate or terephthalate, or polycyclic moieties, e.g.,naphthalenedicarboxylate. Preferably, the aromatic dicarboxylic acidmoieties are isophthalate and/or terephthalate: either or both of saidmoieties may be present. For the most part, both are present in a molarratio of isophthalate to terephthalate in the range of about 0.25-4.0:1,preferably about 0.8-2.5:1.

In the optional soft block units of formula II resorcinol oralkylresorcinol moieties are again present in ester-forming combinationwith R⁵ which is a divalent C₄₋₁₂ aliphatic, alicyclic or mixedaliphatic-alicyclic radical. It is preferably aliphatic and especiallyC₈₋₁₂ straight chain aliphatic. A particularly preferred arylate polymercontaining soft block units is one consisting of resorcinol isophthalateand resorcinol sebacate units in a molar ratio between 8.5:1.5 and9.5:0.5.

Polycarbonates useful in the compositions of the invention include thosecomprising structural units of the formula IV:

wherein at least about 60 percent of the total number of R6 groups arearomatic organic radicals and the balance thereof are aliphatic,alicyclic, or aromatic radicals. More preferably, R⁶ is an aromaticorganic radical and still more preferably a radical of the formula V:

—A¹—Y¹—A²—  (V)

wherein each A¹ and A² is a monocyclic divalent aryl radical and Y¹ is abridging radical in which one or two atoms, separate A¹ from A². Thepreferred embodiment is one in which one atom separates A¹ from A².Illustrative non-limiting examples of radicals of this type are —O—,—S—, —S(O)— or —SO₂)—, —C(O)—, methylene, cyclohexyl-methylene,2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene,cyclopentadecylidene, cyclododecylidene, and adamantylidene. Thebridging radical Y¹, is most often a hydrocarbon group and particularlya saturated group such as methylene, cyclohexylidene,3,3,5-trimethylcyclohexylidene, or isopropylidene.

Preferred polycarbonates are derived from dihydric phenols in which onlyone atom separates A¹ and A². Some illustrative, non-limiting examplesof dihydric phenols include the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438, which is incorporated herein by reference. Somepreferred examples of dihydric phenols include2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A);4,4′-(3,3,5-trimethylcyclohexylidene)diphenol;2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane;2,4′-dihydroxydiphenylmethane; bis(2-hydroxyphenyl)methane;bis(4-hydroxyphenyl)methane; bis(4-hydroxy-5-nitrophenyl)methane;bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane;1,1-bis(4-hydroxyphenyl)ethane; 1,1-bis(4-hydroxy-2-chlorophenyl)ethane;2,2-bis(3-phenyl-4-hydroxyphenyl)-propane;bis(4-hydroxyphenyl)cyclohexylmethane;2,2-bis(4-hydroxyphenyl)-1-phenylpropane; resorcinol; C₁₋₃alkyl-substituted resorcinols, and6,6′-dihydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane.

The most preferred polycarbonates are bisphenol A polycarbonates, inwhich each of A¹ and A² is p-phenylene and Y¹ is isopropylidene.Preferably, the weight average molecular weight of the initialpolycarbonate ranges from about 5,000 to about 100,000; more preferablyfrom about 10,000 to about 65,000, still more preferably from about16,000 to about 40,000, and most preferably from about 20,000 to about36,000. Suitable polycarbonates may be made using any process known inthe art, including interfacial, solution, solid-state, or meltprocesses.

In one embodiment the present invention comprises a compositioncontaining at least one polycarbonate. In another embodiment theinvention comprises compositions containing two differentpolycarbonates. Both homopolycarbonates derived from a single dihydroxycompound monomer and copolycarbonates derived from more than onedihydroxy compound monomer are encompassed. In a preferred embodimentcompositions comprise a bisphenol A homopolycarbonate and acopolycarbonate comprising bisphenol A monomer units and4,4′-(3,3,5-trimethylcyclohexylidene)diphenol monomer units. Preferably,the copolycarbonate comprises 5-65 mole %, more preferably 15-60 mole %,and most preferably 30-55 mole % of4,4′(3,3,5-trimethylcyclohexylidene)diphenol with the remainingdihydroxy monomer being bisphenol A. The weight ratio of bisphenol Apolycarbonate to copolycarbonate comprising bisphenol A monomer unitsand 4,4′-(3,3,5-trimethylcyclohexylidene)diphenol monomer units incompositions of the present invention is preferably between 95:5 and70:30 and more preferably between 85:15 and 75:25.

Also suitable for use in the present invention are polyestercarbonates.The polyestercarbonates may generally be termed copolyesters containingcarbonate groups, carboxylate groups, and aromatic carbocyclic groups inthe polymer chain, in which at least some of the carboxylate groups andat least some of the carbonate groups are bonded directly to ring carbonatoms of the aromatic carbocyclic groups. These polyestercarbonates are,in general, prepared by reacting at least dihydric phenol, at least onedifunctional carboxylic acid or reactive derivative of the acid such asthe acid dihalide, and a carbonate precursor. Suitable dihydric phenolsinclude, but are not limited to, those named or referred to hereinabove.Some illustrative, non-limiting examples of suitable aromaticdicarboxylic acids include phthalic acid, isophthalic acid, terephthalicacid, homophthalic acid, o-, m-, and p-phenylenediacetic acid; and thepolynuclear aromatic acids such as diphenic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and the like.These acids may be used either individually, or as a mixture of two ormore different acids in the preparation of suitable polyestercarbonates.

The polyestercarbonates which find use in the instant invention and themethods for their preparation are well known in the art as disclosed in,for example, U.S. Pat. Nos. 3,030,331; 3,169,121; 3,207,814; 4,194,038;4,156,069; 4,238,596; 4,238,597; 4,487,896; 4,506,065, and in copendingapplication Ser. No. 09/181,902, filed Oct. 29, 1998, and assigned tothe same assignee as the instant application, all of which are herebyincorporated by reference. Among the properties characterizing thesepolymers is a relatively high distortion temperature under load (DTUL)as well as a relatively high impact strength as measured by a notchedIzod test protocol.

The polyarylene ethers are most often polyphenylene ethers havingstructural units of the formula:

wherein each Q² is independently halogen, primary or secondary loweralkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each Q³ is independently hydrogen,halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q².

Both homopolymer and copolymer polyphenylene ethers are included. Thepreferred homopolymers are those containing 2,6-dimethyl-1,4-phenyleneether units. Suitable copolymers include random copolymers containingsuch units in combination with, for example,2,3,6-trimethyl-1,4-phenylene ether units. Also included arepolyphenylene ethers containing moieties prepared by grafting onto thepolyphenylene ether in known manner such materials as vinyl monomers orpolymers such as polystyrenes and elastomers, as well as coupledpolyphenylene ethers in which coupling agents such as low molecularweight polycarbonates, quinones, heterocycles and formals undergoreaction in known manner with the hydroxy groups of two polyphenyleneether chains to produce a higher molecular weight polymer.

The polyphenylene ethers generally have an intrinsic viscosity greaterthan about 0.1, most often in the range of about 0.2-0.6 and especiallyabout 0.35-0.6 deciliters per gram (dl./g.), as measured in chloroformat 25° C.

The polyphenylene ethers are typically prepared by the oxidativecoupling of at least one monohydroxyaromatic compound such as2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are generallyemployed for such coupling; they typically contain at least one heavymetal compound such as a copper, manganese or cobalt compound, usuallyin combination with various other materials.

Particularly useful polyphenylene ethers for many purposes are thosewhich comprise molecules having at least one aminoalkyl-containing endgroup. The aminoalkyl radical is covalently bound to a carbon atomlocated in an ortho position to a hydroxy group. Products containingsuch end groups may be obtained by incorporating an appropriate primaryor secondary monoamine such as di-n-butylamine or dimethylamine as oneof the constituents of the oxidative coupling reaction mixture. Alsofrequently present are 4-hydroxybiphenyl end groups and/or biphenylstructural units, typically obtained from reaction mixtures in which aby-product diphenoquinone is present, especially in acopper-halide-secondary or tertiary amine system. A substantialproportion of the polymer molecules, typically constituting as much asabout 90% by weight of the polymer, may contain at least one of saidaminoalkyl-containing and 4-hydroxy-biphenyl end groups. It will beapparent to those skilled in the art from the foregoing that thepolyphenylene ethers contemplated for use in the invention include allthose presently known, irrespective of variations in structural units orancillary chemical features.

Both homopolymer and copolymer thermoplastic polymers are included inthe compositions of the present invention. Copolymers may includerandom, block or graft type. Thus, for example, suitable polystyrenesinclude homopolymers, such as amorphous polystyrene and syndiotacticpolystyrene, and copolymers. The latter embraces high impact polystyrene(HIPS), a genus of rubber-modified polystyrenes comprising blends andgrafts wherein the rubber is a polybutadiene or a rubbery copolymer ofabout 70-98% styrene and 2-30% diene monomer. Also included are ABScopolymers, which are typically grafts of styrene and acrylonitrile on apreviously formed diene polymer backbone (e.g., polybutadiene orpolyisoprene). Suitable ABS copolymers may be produced by any methodsknown in the art. Especially preferred ABS copolymers are typicallyproduced by mass polymerization (often referred to as bulk ABS) oremulsion polymerization (often referred to as high rubber graft ABS).

The preferred thermoplastic polymers for many purposes are polyesters,polycarbonates, polyphenylene ethers, polystyrene resin, high impactpolystyrene resin (HIPS), and styrene-acrylonitrile copolymers (SAN),including ABS copolymers. These may be employed individually or asblends. Especially preferred blends include those of polyphenylene etherwith at least one of HIPS, amorphous polystyrene, and syndiotacticpolystyrene; and polycarbonate blends with at least one of ABS, SAN, andpolyester.

In resinous compositions there is often an improvement in melt flowand/or other physical properties when one molecular weight grade of atleast one resinous constituent is combined with a relatively lowermolecular weight grade of similar resinous constituent. Illustrative,non-limiting examples include compositions containing polycarbonate,polyphenylene ether, thermoplastic polyester, thermoplastic elastomericpolyester, or polyamide. For example, in a polycarbonate-containingblend there is often an improvement in melt flow when one molecularweight grade of polycarbonate is combined with a proportion of arelatively lower molecular weight grade of similar polycarbonate.Therefore, the present invention encompasses compositions comprisingonly one molecular weight grade of a particular resinous constituent andalso compositions comprising two or more molecular weight grades ofsimilar resinous constituent. When two or more molecular weight gradesof similar resinous constituent are present, then the weight averagemolecular weight of the lowest molecular weight constituent is about 10%to about 95%, preferably about 40% to about 85%, and more preferablyabout 60% to about 80% of the weight average molecular weight of thehighest molecular weight constituent. In one representative,non-limiting embodiment polycarbonate-containing blends include thosecomprising a polycarbonate with weight average molecular weight betweenabout 28,000 and about 32,000 combined with a polycarbonate with weightaverage molecular weight between about 16,000 and about 26,000. When twoor more molecular weight grades of similar resinous constituent arepresent, the weight ratios of the various molecular weight grades mayrange from about 1 to about 99 parts of one molecular weight grade andfrom about 99 to about 1 parts of any other molecular weight grades. Amixture of two molecular weight grades of a resinous constituent isoften preferred, in which case the weight ratios of the two grades mayrange from about 99:1 to about 1:99, preferably from about 80:20 toabout 20:80, and more preferably from about 70:30 to about 50:50. Sincenot all manufacturing processes for making a particular resinousconstituent are capable of making all molecular weight grades of thatconstituent, the present invention encompasses compositions comprisingtwo or more molecular weight grades of similar resinous constituent inwhich each of the similar resins is made by a different manufacturingprocess. In one particular embodiment the instant invention encompassescompositions comprising a polycarbonate made by an interfacial processin combination with a polycarbonate of different weight averagemolecular weight made by a melt process.

Another constituent of the resin compositions of the invention is atleast one phosphoramide having a glass transition point of at leastabout 0° C., preferably of at least about 10° C., and most preferably ofat least about 20° C., of the formula I:

wherein Q¹ is oxygen or sulfur; R¹ is an amine residue, and R² and R³are each independently an alkyloxy, alkylthio, aryloxy, or arylthioresidue, or an aryloxy or arylthio residue containing at least one alkylor halogen substitution, or mixture thereof; or an amine residue.

It should be noted that in the descriptions herein, the words “radical”and “residue” are used interchangeably, and are both intended todesignate an organic moiety. For example, alkyl radical and alkylresidue are both intended to designate an alkyl moiety. The term “alkyl”as used in the various embodiments of the present invention is intendedto designate both normal alkyl, branched alkyl, aralkyl, and cycloalkylradicals. Normal and branched alkyl radicals are preferably thosecontaining from 1 to about 12 carbon atoms, and include as illustrativenon-limiting examples methyl, ethyl, propyl, isopropyl, butyl,tertiary-butyl, pentyl, neopentyl, and hexyl. Cycloalkyl radicalsrepresented are preferably those containing from 3 to about 12 ringcarbon atoms. Some illustrative non-limiting examples of thesecycloalkyl radicals include cyclobutyl, cyclopentyl, cyclohexyl,methylcyclohexyl, and cycloheptyl. Preferred aralkyl radicals are thosecontaining from 7 to about 14 carbon atoms; these include, but are notlimited to, benzyl, phenylbutyl, phenylpropyl, and phenylethyl. Arylradicals used in the various embodiments of the present invention arepreferably those containing from 6 to 12 ring carbon atoms. Someillustrative non-limiting examples of these aryl radicals includephenyl, biphenyl, and naphthyl. The preferred halogen radicals used inthe various embodiments of the present invention are chlorine andbromine.

The compositions may contain essentially a single phosphoramide or amixture of two or more different types of phosphoramides. Compositionscontaining essentially a single phosphoramide are preferred.

When a phosphoramide having a glass transition point of at least about0° C. is used as a source of phosphorus in resin compositions, it wasunexpectedly found that a higher heat deflection temperature of testspecimens made from the resin composition could be obtained as comparedto compositions containing an organophosphate known in the art forenhancing the processability and/or flame resistance characteristics ofthe composition.

Although the invention is not dependent upon mechanism, it is believedthat selection of R¹, R², and R³ residues that result in restrictedrotation of the bonds connected to the phosphorus provide an increasedglass transition point in comparison to similar phosphoramides withresidues having a lesser degree of restriction. Residues having bulkysubstituents such as, for example, aryloxy residues, particularly thosecontaining at least one halogen or preferably at least one alkylsubstitution, result in phosphoramides having a higher glass transitionpoint than similar phosphoramides without aryloxy residues. Likewise,residues wherein at least two of the R¹, R², and R³ residues areinterconnected, such as a neopentyl residue for the combination of theR² and R³ residues, can lead to desired phosphoramides having a glasstransition point of at least about 0° C.

In a preferred embodiment, the phosphoramide comprises a phosphoramidehaving a glass transition temperature of at least about 0° C.,preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula VI:

wherein each Q¹ is independently oxygen or sulfur; and each of A³⁻⁶ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue. In a preferredembodiment each Q¹ is oxygen, and each A³⁻⁶ is an aryloxy moiety with atleast one aryloxy moiety having at least one substituent on an aromaticring ortho to the oxygen linkage. In a more preferred embodiment each Q¹is oxygen, and each A³⁻⁶ moiety is independently an aryloxy moiety withat least one substituent on each aromatic ring ortho to the oxygenlinkage, optionally further substituted. In a still more preferredembodiment each Q¹ is oxygen, and each A³⁻⁶ moiety is independently anaryloxy moiety with at least two substituents on each aromatic ringortho to the oxygen linkage, as for example a 2,6-disubstituted phenoxymoiety, optionally further substituted. Preferred substituents are C₁₋₈straight-chain or branched alkyl, or halogen. In an especially preferredembodiment of the invention, each Q¹ is oxygen, and each A³⁻⁶ moiety isindependently phenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or2,4,6-trimethylphenoxy. In a more especially preferred embodiment of theinvention, each Q¹ is oxygen, and all A³⁻⁶ moieties are phenoxy,2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy.These phosphoramides are piperazine-type phosphoramides. In the aboveformula wherein each Q¹ is oxygen, and each A³⁻⁶ moiety is a2,6-dimethylphenoxy moiety, the glass transition temperature of thephosphoramide is about 62° C. and the melting point is about 192° C.Also, in the above formula wherein each Q¹ is oxygen, and each A³⁻⁶moiety is a 2,3,6-trimethylphenoxy moiety, the glass transitiontemperature of the phosphoramide is about 61° C. and the melting pointis about 237-239° C. Also, in the above formula wherein each Q¹ isoxygen, and each A³⁻⁶ moiety is a 2,4,6-trimethylphenoxy moiety, theglass transition temperature of the phosphoramide is about 74° C. andthe melting point is about 233-234° C. Conversely, in the above formulawherein each Q¹ is oxygen, and each A³⁻⁶ moiety is phenoxy, the glasstransition temperature of the phosphoramide is about 0° C. and themelting point is about 188° C. It was unexpected that the glasstransition temperature would be so high for a sterically hinderedphosphoramide of formula VI where each Q¹ is oxygen, and wherein each ofA³⁻⁶ is a 2,6-dimethylphenoxy moiety (i.e. about 62° C.) as compared tothe glass transition temperature of the corresponding phosphoramide offormula VI wherein each Q¹ is oxygen, and each of A³⁻⁶ is a phenoxymoiety (i.e. about 0° C.), especially since the melting points for thephosphoramides differ by only about 4° C. For comparison, the glasstransition temperature of tetraphenyl resorcinol diphosphate is about−38° C. It is also possible to make phosphoramides with intermediateglass transition temperatures by using a mixture of various substitutedand non-substituted aryl moieties within the phosphoramide.

In another preferred embodiment, the phosphoramide comprises aphosphoramide having a glass transition temperature of at least about 0°C., preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula VII:

wherein each Q¹ is independently oxygen or sulfur; and each of A⁷⁻¹¹ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue optionally containing at least one alkylor halogen substitution, or mixture thereof; or an amine residue; and nis from 0 to about 200. In a preferred embodiment each Q¹ is oxygen, andeach A⁷⁻¹¹ moiety is independently phenoxy or a substituted phenoxymoiety. In a more preferred embodiment each Q¹ is oxygen, and each A⁷⁻¹¹is an aryloxy moiety with at least one aryloxy moiety having at leastone substituent on an aromatic ring ortho to the oxygen linkage. In astill more preferred embodiment each Q¹ is oxygen, and each A⁷⁻¹¹ moietyis independently an aryloxy moiety with at least one substituent on eacharomatic ring ortho to the oxygen linkage, optionally furthersubstituted. In a still more preferred embodiment each Q¹ is oxygen, andeach A⁷⁻¹¹ moiety is independently an aryloxy moiety with at least twosubstituents on each aromatic ring ortho to the oxygen linkage, as forexample a 2,6-disubstituted phenoxy moiety, optionally furthersubstituted. Preferred substituents are C₁₋₈ straight-chain or branchedalkyl, or halogen. In an especially preferred embodiment of theinvention, each Q¹ is oxygen, and each A⁷⁻¹¹ moiety is independentlyphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy,or 2,4,6-trimethylphenoxy, and n is from 0 to about 5. In a moreespecially preferred embodiment of the invention, each Q¹ is oxygen, andall A⁷⁻¹¹ moieties are phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy, and n is from 0 toabout 5.

In another embodiment of the invention the phosphoramide comprises aphosphoramide having a glass transition temperature of at least about 0°C., preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula VIII:

wherein each Q¹ is independently oxygen or sulfur; and each of A¹²⁻¹⁷ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue optionally containing at least one alkylor halogen substitution, or mixture thereof; or an amine residue. In apreferred embodiment each Q¹ is oxygen, and each A¹²⁻¹⁷ moiety isindependently phenoxy or a substituted phenoxy moiety. In a morepreferred embodiment each Q¹ is oxygen, and each A¹²⁻¹⁷ is an aryloxymoiety with at least one aryloxy moiety having at least one substituenton an aromatic ring ortho to the oxygen linkage. In a still morepreferred embodiment each Q¹ is oxygen, and each A¹²⁻¹⁷ moiety isindependently an aryloxy moiety with at least one substituent on eacharomatic ring ortho to the oxygen linkage, optionally furthersubstituted. In yet a still more preferred embodiment each Q¹ is oxygen,and each A¹²⁻¹⁷ moiety is independently an aryloxy moiety with at leasttwo substituents on each aromatic ring ortho to the oxygen linkage, asfor example a 2,6-disubstituted phenoxy moiety, optionally furthersubstituted. Preferred substituents are C₁₋₈ straight-chain or branchedalkyl, or halogen. In an especially preferred embodiment of theinvention, each Q¹ is oxygen, and each A¹²⁻¹⁷ moiety is independentlyphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy,or 2,4,6-trimethylphenoxy. In a more especially preferred embodiment ofthe invention, each Q¹ is oxygen, and all A¹²⁻¹⁷ moieties are2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or2,4,6-trimethylphenoxy.

In another embodiment of the invention the phosphoramide comprises aphosphoramide having a glass transition temperature of at least about 0°C., preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula IX:

wherein each Q¹ is independently oxygen or sulfur; each of A¹⁸⁻²¹ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue optionally containing at least one alkylor halogen substitution, or mixture thereof; or an amine residue; andeach R⁷ is an alkyl radical, or both R⁷ radicals taken together are analkylidene or alkyl-substituted alkylidene radical. In preferredembodiments each Q¹ is oxygen, and each A¹⁸⁻²¹ moiety is independentlyphenoxy or a substituted phenoxy moiety. In a more preferred embodimenteach Q¹ is oxygen, and each A¹⁸⁻²¹ is an aryloxy moiety with at leastone aryloxy moiety having at least one substituent on an aromatic ringortho to the oxygen linkage. In still more preferred embodiments each Q¹is oxygen, and each A¹⁸⁻²¹ moiety is independently an aryloxy moietywith at least one substituent on each aromatic ring ortho to the oxygenlinkage, optionally further substituted. In yet still more preferredembodiments each Q¹ is oxygen, and each A¹⁸⁻²¹ moiety is independentlyan aryloxy moiety with at least two substituents on each aromatic ringortho to the oxygen linkage, as for example a 2,6-disubstituted phenoxymoiety, optionally further substituted. Preferred substituents are C₁₋₈straight-chain or branched alkyl, or halogen. In especially preferredembodiments of the invention, each Q¹ is oxygen, and each A¹⁸⁻²¹ moietyis independently phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy. In a particularlypreferred embodiment, each Q¹ is oxygen; both R⁷ radicals taken togetherare an unsubstituted (CH₂)_(m) alkylidene radical, wherein m is 2 to 10;and each A¹⁸⁻²¹ moiety is independently an aryloxy moiety with at leastone substituent on each aromatic ring ortho to the oxygen linkage,optionally further substituted, especially 2-methylphenoxy,2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy.In an especially preferred embodiment, each Q¹ is oxygen; each R⁷ ismethyl; and each A¹⁸⁻²¹ moiety is independently an aryloxy moiety withat least one substituent on each aromatic ring ortho to the oxygenlinkage, optionally further substituted, especially 2-methylphenoxy,2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy.

In another embodiment of the invention, the phosphoramide comprises aphosphoramide having a glass transition point of at least about 0° C.,preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula I:

wherein Q¹ is oxygen or sulfur, and R¹ is of the formula X:

wherein each Q¹ is independently oxygen or sulfur; each of A²²⁻²⁴ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue optionally containing at least one alkylor halogen substitution, or mixture thereof; or an amine residue; eachZ¹ is an alkyl radical, aromatic radical, or aromatic radical containingat least one alkyl or halogen substitution or mixture thereof; each X¹is an alkylidene radical, aromatic radical, or aromatic radicalcontaining at least one alkyl or halogen substitution or mixturethereof; n is from 0 to about 200; and R² and R³ are each independentlyan alkyloxy, alkylthio, aryloxy, or arylthio residue, or an aryloxy orarylthio residue optionally containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue. In preferredembodiments each Q¹ is oxygen, and each A²²⁻²⁴ moiety and each R²⁻³moiety is independently phenoxy or a substituted phenoxy moiety. In morepreferred embodiments each Q¹ is oxygen, and each A²²⁻²⁴ moiety and eachR²⁻³ moiety is independently an aryloxy moiety with at least one aryloxymoiety having at least one substituent on an aromatic ring ortho to theoxygen linkage, optionally further substituted. In still more preferredembodiments each Q¹ is oxygen, and each A²²⁻²⁴ moiety and each R²⁻³moiety is independently an aryloxy moiety with at least one substituenton each aromatic ring ortho to the oxygen linkage, optionally furthersubstituted. In yet still more preferred embodiments each Q¹ is oxygen,and each A²²⁻²⁴ moiety and each R²⁻³ moiety is independently an aryloxymoiety with at least two substituents on each aromatic ring ortho to theoxygen linkage, as for example a 2,6-disubstituted phenoxy moiety,optionally further substituted. Preferred substituents are C₁₋₈straight-chain or branched alkyl, or halogen. In an especially preferredembodiment, each Q¹ is oxygen; each A²²⁻²⁴ moiety is independentlyphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy,or 2,4,6-trimethylphenoxy; each Z¹ is methyl or benzyl; each X¹ is analkylidene radical containing 2-24 carbon atoms; n is from 0 to about 5;and R² and R³ are each independently phenoxy, 2-methylphenoxy,2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy.

In another embodiment of the invention, the phosphoramide comprises aphosphoramide having a glass transition point of at least about 0° C.,preferably of at least about 10° C., and most preferably of at leastabout 20° C., of the formula I:

wherein Q¹ is oxygen or sulfur; and R¹ is of the formula XI:

wherein each Q¹ is independently oxygen or sulfur; each X² is analkylidene or alkyl-substituted alkylidene residue, aryl residue, oralkaryl residue; each Z² is an alkylidene or alkyl-substitutedalkylidene residue; each of R⁸, R⁹, and R¹⁰ is independently analkyloxy, alkylthio, aryloxy, or arylthio residue, or an aryloxy orarylthio residue optionally containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue; n is from 0 toabout 5; and R² and R³ are each independently an alkyloxy, alkylthio,aryloxy, or arylthio residue, or an aryloxy or arylthio residueoptionally containing at least one alkyl or halogen substitution, ormixture thereof; or an amine residue. In preferred embodiments each Q¹is oxygen, and each R⁸⁻¹⁰ moiety and each R²⁻³ moiety is independentlyphenoxy or a substituted phenoxy moiety. In more preferred embodimentseach Q¹ is oxygen, and each R⁸⁻¹⁰ moiety and each R²⁻³ moiety isindependently an aryloxy moiety with at least one aryloxy moiety havingat least one substituent on an aromatic ring ortho to the oxygenlinkage, optionally further substituted. In still more preferredembodiments each Q¹ is oxygen, and each R⁸⁻¹⁰ moiety and each R²⁻³moiety is independently an aryloxy moiety with at least one substituenton each aromatic ring ortho to the oxygen linkage, optionally furthersubstituted. In yet still more preferred embodiments each Q¹ is oxygen,and each R⁸⁻¹⁰ moiety and each R²⁻³ moiety is independently an aryloxymoiety with at least two substituents on each aromatic ring ortho to theoxygen linkage, as for example a 2,6-disubstituted phenoxy moiety,optionally further substituted. Preferred substituents are C₁₋₈straight-chain or branched alkyl, or halogen. In a particularlypreferred embodiment, each Q¹ is oxygen; each X² is an alkylidene oralkyl-substituted alkylidene residue; each Z² is an alkylidene oralkyl-substituted alkylidene residue; each of R², R³, R⁸, R⁹, and R¹⁰ isindependently phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy; and n is from 0 toabout 5. In a more particularly preferred embodiment, each Q¹ is oxygen;each X² and Z² is independently an unsubstituted alkylidene residue ofthe form (CH₂)_(m), wherein m is 2 to 10; each of R², R³, R⁸, R⁹, andR¹⁰ is independently phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy; and n is from 0 toabout 5. In especially preferred embodiments, the phosphoramide isderived from piperazine (i.e. X² and Z² are each —CH₂—CH₂—).

In another preferred embodiment, the phosphoramide comprises a cyclicphosphoramide having a glass transition point of at least about 0° C.,preferably of at least about 10° C., and most preferably of at leastabout 20° C. of the formula XII:

wherein each of R¹¹⁻¹⁴ is independently a hydrogen, an alkyl radical, orhalogen, X³ is an alkylidene radical, Q¹ is oxygen or sulfur, and A²⁵ isa group derived from a primary or secondary amine having the same ordifferent radicals that can be aliphatic, alicyclic, aromatic, oralkaryl, or A²⁵ is a group derived from a heterocyclic amine, or A²⁵ isa hydrazine compound. Preferably Q¹ is oxygen. In preferred embodimentseach Q¹ is oxygen, and each of the two phenyl rings is independently atleast a monosubstituted phenoxy moiety, wherein the at least onesubstituent is represented by the linkage to X³. In still more preferredembodiments each Q¹ is oxygen, and each of the two phenyl rings isindependently at least disubstituted wherein at least one substituent isrepresented by the linkage to X³. Preferred substituents R¹¹⁻¹⁴, whenpresent, are straight-chain or branched alkyl, or halogen. In apreferred embodiment R¹¹⁻¹⁴ substituents on each aromatic ring are each2,4-dimethyl or 2,3-dimethyl groups relative to the oxygen linkage. In amore preferred embodiment R¹¹ and R¹³ are each methyl ortho to theoxygen linkage, and R¹² and R¹⁴ are each hydrogen. In a still morepreferred embodiment R¹¹⁻¹⁴ are hydrogen. It should be noted that when nis 0, then the two aryl rings are linked together at that site (i.e.where X³ is absent) by a single bond in the positions ortho,ortho' tothe phosphoryl bonds.

In another preferred embodiment, the phosphoramide comprises abis(cyclic) phosphoramide having a glass transition point of at leastabout 0° C., preferably of at least about 10° C., and most preferably ofat least about 20° C. of the formula XIII:

wherein Q¹ is oxygen or sulfur; each of R¹⁵⁻²² is independently ahydrogen, an alkyl radical, or halogen; X⁴ is an alkylidene radical; mand n are each independently 0 or 1; and A²⁶ is

wherein G¹ is sulfur, an alkylidene radical, alkyl-substitutedalkylidene radical, aryl radical, or alkaryl radical, and each Z³ isindependently an alkyl radical, an aryl radical, or an aryl radicalcontaining at least one alkyl or halogen substitution, or mixturethereof; or wherein A²⁶ is

wherein G² is alkylidene, aryl, or alkaryl, and Y² is alkylidene oralkyl-substituted alkylidene. In preferred embodiments each Q¹ isoxygen, and each of the four phenyl rings is independently at least amonosubstituted phenoxy moiety, wherein the at least one substituent isrepresented by the linkage to X⁴. In still more preferred embodimentseach Q¹ is oxygen, and each of the two phenyl rings is independently atleast disubstituted wherein at least one substituent is represented bythe linkage to X⁴. Preferred substituents R¹⁵⁻²², when present, arestraight-chain or branched alkyl, or halogen. In a preferred embodimentR¹⁵⁻²² substituents on each aromatic ring are each 2,4-dimethyl or2,3-dimethyl groups relative to the oxygen linkage. In a more preferredembodiment R¹⁵, R¹⁷, R¹⁹, and R²¹ are each methyl ortho to the oxygenlinkage, and R¹⁶, R¹⁸, R²⁰, and R²² are each hydrogen. In a still morepreferred embodiment R¹⁵⁻²² are hydrogen. Highly preferredphosphoramides include those wherein Q¹ is oxygen; A²⁶ is a residue ofpiperazine; the phosphoramide has a plane of symmetry through A²⁶;R¹⁵⁻²² are hydrogen; n and m are each 1; and X⁴ is CHR²³ wherein R²³ isa hydrogen or an alkyl residue of from about 1 to about 6 carbon atoms.It should be noted that when either or both of m or n is 0, then the twoaryl rings are linked together at that site (i.e. where X⁴ is absent) bya single bond in the positions ortho,ortho' to the phosphoryl bonds.

Phosphoramides of useful molecular structure are preferably prepared bythe reaction of a corresponding amine such as, for example, piperazineor N,N′-dimethylethylenediamine with a diaryl chlorophosphate of theformula (aryl-O)₂POCl in the presence of a tertiary amine. This methodof preparation is described in Talley, J. Chem. Eng. Data, 33, 221-222(1988) and leads to specific phosphoramide compounds without repeatingunits. Alternatively, phosphoramides may be prepared by the reaction ofthe corresponding amine with P(O)Cl₃ in the presence of a tertiaryamine, with the desired hydroxyl-or thiohydroxy-containing compoundadded simultaneously or subsequently to the addition of the amine.Addition of a diamine or triamine to P(O)Cl₃ with simultaneous orsubsequent addition of the hydroxyl or thiohydroxy-containing compoundis believed to lead to repeating units of phosphoramide, often of 1 toabout 5 phosphoramide linkages per compound. Similarly, addition of adiamine or triamine to a monosubstituted phosphoryl- or thiophosphoryldichloride with simultaneous or subsequent addition of hydroxyl- orthiohydroxy-containing compound is also believed to lead to repeatingunits of phosphoramide. P(S)Cl₃ may be substituted for P(O)Cl₃ in theabove preparations to provide suitable phosphoramides.

Another constituent of the resin compositions of the invention is atleast one adjunct flame retardant compound. An adjunct flame retardantcompound may be an organic or inorganic, polymeric or non-polymericcompound. In certain preferred embodiments an adjunct flame retardant isone which may promote char formation in at least one resinousconstituent, for example in polycarbonate when polycarbonate is a blendconstituent.

In one embodiment of the present invention the adjunct flame retardantcomprises at least one polymeric or non-polymeric organic phosphorusspecies selected from the group consisting of phosphate esters,thiophosphate esters, phosphonate esters, thiophosphonate esters,phosphinate esters, thiophosphinate esters, phosphines, includingtriphenylphosphine, phosphine oxides, including triphenylphosphine oxideand tris(2-cyanoethyl)phosphine oxide, thiophosphine oxides, andphosphonium salts. Preferred organic phosphorus species arenon-polymeric phosphate esters including, for example, alkyl phosphateesters, aryl phosphate esters, resorcinol-based phosphate esters, andbisphenol-based phosphate esters. Illustrative, non-limiting examples ofsuch phosphorus species include triphenylphosphate, tricresylphosphate,resorcinol bis(diphenyl-phosphate), bisphenol A bis(diphenyl-phosphate),and other aromatic phosphate esters known in the art.

In another embodiment of the present invention the adjunct flameretardant comprises at least one polymeric or non-polymeric inorganicphosphorus salt with anions selected from the group consisting ofphosphates, thiophosphates, phosphonates, thiophosphonates,phosphinates, thiophosphinates, pyrophosphates, and metaphosphates. Thecations in these inorganic phosphorus salts comprise at least one cationselected from the group consisting of ammonium, alkyl-substitutedammonium, aryl-substituted ammonium, and mixed alkyl-aryl-substitutedammonium; alkali metal, lithium, sodium, potassium; alkaline earthmetal, magnesium, calcium, barium; transition metal, zirconium, hafnium,iron, zinc; lanthanide metal, lanthanum; boron; aluminum; and tin.Preferred inorganic phosphorus species are non-polymeric phosphate saltsincluding, for example, alkali metal phosphates, boron phosphate,aluminum phosphate, and zinc phosphate.

In another embodiment of the present invention the adjunct flameretardant comprises at least one polymeric or non-polymeric sulfurspecies selected from the group consisting of sulfonate salts, sulfinatesalts, sulfones, sulfoxides, and sulfides. Illustrative, non-limitingexamples of such polymeric or non-polymeric sulfur species includepolyarylene sulfide, polyarylene sulfide-sulfones, and salts ofsulfonated aromatic compounds. Preferred sulfur species arepolyphenylene sulfide, polyphenylsulfone, sodium para-toluene sulfonate,potassium diphenylsulfone-3-sulfonate, and Reimer's salts, includingpotassium perfluorobutane sulfonate.

In another embodiment of the present invention the adjunct flameretardant comprises at least one polymeric or non-polymericboron-containing species. Illustrative, non-limiting examples of suchspecies include zinc borate, boron phosphate, borax, and boric acid.Zinc borate is a particularly preferred boron-containing species.

In yet another embodiment of the present invention the adjunct lameretardant comprises at least one polymeric or non-polymeric antimonysalt selected from the group consisting of oxides, halides, sulfides,sulfonates, phosphates, phosphonates, and carboxylates. Illustrative,non-limiting examples of such polymeric or non-polymeric antimony saltsinclude antimony oxide, antimony trichloride, and antimony potassiumtartrate. A particularly preferred antimony salt is antimony oxide.

In yet another embodiment of the present invention the adjunct flameretardant comprises at least one polymeric or non-polymeric siliconecompound. Polymeric silicone compounds are often preferred. In oneembodiment of the present invention particularly preferred polysiloxanesare those containing a plurality of dimethylsiloxane units, and,optionally, a minor proportion of organic groups, including but notlimited to, at least one of vinyl, hydrogen, epoxy, amine, phenyl, andthe like. For certain embodiments suitable polymeric silicone compoundsinclude SF1706 and SF1708 available from General Electric Silicones. Inanother embodiment further preferred polysiloxanes are those which havefirst units of RSiO_(1.0) and second units of RSiO^(1.5) where R is aradical selected from the group consisting of saturated and aromaticring hydrocarbon groups as disclosed in European Patent Application829,521, which is incorporated herein by reference.

In another embodiment of the present invention the adjunct flameretardant comprises at least one organoclay. Examples of compositionscontaining organoclays are disclosed in copending, commonly ownedapplication Ser. No. 09/032,533, filed Feb. 27, 1998.

As used herein, “organoclay” means a layered clay, usually a silicateclay, derived from a layered mineral and in which organic moieties havebeen incorporated, ordinarily by ion exchange and especially cationexchange with organic ions and/or onium compounds. Illustrative organicions are mono-and polyammonium cations such as trimethyldodecylammoniumand N,N′-didodecylimidazolium.

Illustrative layered minerals are the kaolinites and themontmorillonites. It is also possible to employ minerals of the illitegroup, including hydromicas, phengite, brammallite, glaucomite,cejadonite and the like. Often, the preferred layered minerals includethose often referred to as 2:1 layered silicate minerals, includingmuscovite, vermiculite, saponite, hectorite and montmorillonite, thelatter often being most preferred. The layered minerals may besynthetically produced, but most often they are naturally occurring andcommercially available. A detailed description of suitable layeredminerals can be found in U.S. Pat. No. 5,530,052, the disclosure ofwhich is incorporated by reference herein.

Suitable specific commercially available or easily prepared organoclayswhich are illustrative of those which may be employed include CLAYTONEHY, a montmorillonite which has been cation exchanged withdimethyidi(hydrogenated tallow)ammonium ion, and CLAYTONE APA, amontmorillonite which has been cation exchanged withmethylbenzyldi(hydrogenated tallow)ammonium ion, both available fromSouthern Clay Products; and montmorillonite which has been cationexchanged with such ions as dodecylammonium, trimethyldodecylammonium,N,N′-didodecylimidazolium, N,N′-ditetradecylbenzimidazolium ormethylbis(hydroxyethyl)-(hydrogenated tallow)ammonium.

In one embodiment of the invention the combination of adjunct flameretardant and at least one phosphoramide having a glass transition pointof at least about 0° C. results in a flame retardant composition havinga UL-94 rating of V-2, V-1, or V-0. In another embodiment of theinvention the presence of certain amounts of adjunct flame retardantpermits the use of a lesser amount of at least one phosphoramide havinga glass transition point of at least about 0° C. without substantialloss in flame retardant properties of the composition. Withoutsubstantial loss in flame retardant properties of the composition meansthat the UL-94 rating for the composition does not become worse in thepresence of phosphoramide/adjunct flame retardant combination comparedto that rating observed in the absence of adjunct flame retardant. AUL-94 rating becomes worse, for example, when it increases from V-0 toeither V-1 or V-2, or when it increases from V-1 to V-2. In yet anotherembodiment of the invention the flame retardant properties of thecomposition become better in the presence of phosphoramide/adjunct flameretardant combination compared to those observed in the absence ofadjunct flame retardant. Better flame retardant properties mean thateither the flame out time (defined hereinafter below) for thecomposition decreases and/or that the UL-94 rating for the compositionimproves, for example, from V-2 to either V-1 or V-0, or from V-1 toV-0. In still another embodiment of the invention a synergistic effecton composition properties, particularly flame retardant properties, isobserved in the presence of the phosphoramide/adjunct flame retardantcombination compared to that observed in the presence of at least onephosphoramide or adjunct flame retardant alone.

The resinous compositions of this invention may contain a flameretarding amount and/or processability enhancing amount of thecombination of at least one phosphoramide and adjunct flame retardant.Flame retardancy may be measured according to the Underwriters'Laboratory UL-94 protocol. In this embodiment a flame retarding amountis an amount effective to render the composition at least a V-2 rating,preferably at least a V-1 rating, and most preferably a V-0 rating aftertesting in the UL-94 protocol when measured on a test specimen of about0.03 to about 0.125 inch in thickness by about 0.5 inch by about 5 inch,preferably about 0.125 inch in thickness by about 0.5 inch by about 5inch, more preferably about 0.06 inch in thickness by about 0.5 inch byabout 5 inch, and most preferably about 0.03 inch in thickness by about0.5 inch by about 5 inch dimensions. Enhanced processability can bedetermined, for example, as a reduction in extruder torque duringcompounding, reduced pressure in injection molding, reduced viscosity,and/or decreased cycle time.

In addition there are many different government-mandated tests forevaluating the fire resistance of thermoplastics, such as polycarbonatesheet building materials. One of the more aggressive tests is Frenchnorm NF-P-92-505 (Norme Francaise NF-P-92-505 of L'Association Francaisede Normalisation (AFNOR), Paris, France). In this test, a radiator isplaced above a specimen of the test material supported on a grid. Cottonwool is placed in a receptacle below the test material. During the test,the radiator is turned on for 10 minutes, and droplets from the specimenmay fall through the grid onto the cotton wool. If the cotton woolburns, the specimen is considered as failing the test.

Therefore, in still another embodiment the resinous compositions of thisinvention may contain an amount of the combination of at least onephosphoramide and at least one adjunct flame retardant effective toprovide at least a 50% pass rate in ten test specimens in Frenchflammability test NF-P-92-505 when measured on test specimens withdensity between about 1.2 to about 6.0 kilograms per square meter. Fortypical sheet material test specimens comprising bisphenol Apolycarbonate a density between about 1.2 to about 6.0 kilograms persquare meter corresponds to a thickness of between about 1.0 to about5.0 millimeters. In a preferred embodiment a test specimen comprisingbisphenol A polycarbonate has a density of about 3.6 kilograms persquare meter and a corresponding thickness of about 3 millimeters.

Typically, a flame retarding amount of the combination of at least onephosphoramide and at least one adjunct flame retardant in thecompositions of the invention is in the range of about 0.008-5 parts,preferably about 0.1-2.5 parts, of phosphorus per 100 parts of resinousmaterials (phr), all percentages herein being by weight. In especiallypreferred embodiments a flame retarding amount of the combination of atleast one phosphoramide and at least one adjunct flame retardant in thecompositions of the invention is in the range of about 0.05-0.2 parts ofphosphorus per 100 parts of resinous materials (phr). The total amountof phosphoramide and adjunct flame retardant is most often in the rangeof about 0.1-50 phr, preferably about 0.5-35 phr, and more preferablyabout 1-25 phr.

In one embodiment of the present invention halogen-containing flameretardants or other halogen-containing species may also be present inthe compositions as adjunct flame retardants. In many resinouscompositions, the combination of a halogen-containing flame retardantand at least one phosphoramide (or mixture of phosphoramide with anotheradjunct flame retardant), particularly including a phosphoramide havinga glass transition point of at least about 0° C., provides both suitableflame retardant properties and unexpectedly improved high temperatureproperties (such as measured, for example, by HDT or Tg of a resinousphase). Illustrative, non-limiting examples of halogen-containing flameretardants or halogen-containing species include brominated flameretardants and phosphoramides containing halogenated aromaticsubstituents. Due to environmental regulations chlorine-free andbromine-free compositions may be preferred for certain applications.Therefore, in a preferred embodiment the present invention includescompositions comprising a thermoplastic resin, at least onephosphoramide having a glass transition point of at least about 0° C.,and an adjunct flame retardant, said compositions being essentially freeof chlorine and bromine. In this context essentially free means that nochlorine- or bromine-containing species has been added to thecompositions in their formulation. In another of its embodiments thepresent invention includes articles obtained from said chlorine-free orbromine-free compositions.

The compositions of the invention may also contain other conventionaladditives including stabilizers, inhibitors, plasticizers, fillers, moldrelease agents, and anti-drip agents. Anti-drip agents are illustratedby tetrafluoroethylene polymers or copolymers, including mixtures withsuch other polymers as polystyrene-co-acrylonitrile (sometimes referredto herein as styrene-acrylonitrile copolymer).

A principal characteristic of preferred compositions of the invention istheir improved high temperature properties. These are demonstrated bythe fact that the decrease in glass transition temperature (Tg)exhibited as a result of the incorporation of a phosphoramide in thecomposition is substantially less than the corresponding decreaseexhibited in blends containing, for example, phosphate esters such asbis(diaryl phosphates) of dihydroxyaromatic compounds. This is evidentwhen a phosphoramide is compared to the organic phosphate ester inamounts suitable to provide enhanced flame resistance when measured, forexample, in the UL-94 test procedure. In the case of phase-separatedblends such as polycarbonate-ABS blends, the decrease in Tg is noted inthe polycarbonate phase.

Experience has shown that the flame retarding properties of aphosphorus-based compound included in a resinous composition aregenerally proportional to the amount of phosphorus in the compositionrather than to the amount of the compound itself. Thus, equal weights oftwo additives having different molecular weights but the same flameretarding properties may produce different UL-94 results, but amounts ofthe two additives which contribute the same proportion of phosphorus tothe resinous composition will produce the same UL-94 results. On theother hand, other physical properties such as high temperatureresistance are dependent on the amount of the compound itself andrelatively independent of the phosphorus proportion therein. For thisreason, the dependence of flame retarding and high temperatureresistance of compositions containing two phosphorus-based compounds maynot follow the same pattern.

It has been shown, however, with respect to the preferred phosphoramidesemployed according to the present invention that their superiorproperties of flame retardance and high temperature resistance areconsistent. Thus, for example, proportions of resorcinolbis(di-2,6-xylyl phosphate) effective to confer a suitable flame-outtime on certain resinous compositions are similar to those produced by atypical bis(2,6-xylyl)-phosphoramide at an essentially equivalent levelof phosphorus, but the bisphosphoramide has a substantially lowertendency to decrease heat deflection temperature (HDT) despite theslightly greater amount of the bulk additive.

It should be clear that the present invention also affords methods toincrease the heat distortion temperature of flame resistant compositionscontaining an amount of at least one phosphoramide and at least oneadjunct flame retardant effective to render the composition a flamerating of at least V-2, preferably of at least V-1, most preferably V-0,in the UL-94 protocol, wherein the method comprises combining at leastone thermoplastic resin, at least one phosphoramide having a glasstransition point of at least about 0° C., preferably of at least about10° C., and most preferably of at least about 20° C.; and at least oneadjunct flame retardant. In a preferred embodiment the invention alsoaffords methods to increase the heat distortion temperature ofchlorine-free and bromine-free, flame resistant compositions asdescribed in the previous sentence. The method may be used to increasethe heat distortion temperature of compositions comprising essentially asingle phosphoramide or a mixture of two or more different types ofphosphoramide; and those comprising essentially a single adjunct flameretardant, or a mixture of two or more different types of adjunct flameretardant. Compositions containing essentially a single phosphoramideand a single adjunct flame retardant are often preferred. Usefulthermoplastic resins have been described herein. Especially preferredthermoplastic resins are polycarbonate, most especially bisphenol A-based polycarbonate, and blends of polycarbonate, especiallypolycarbonate-SAN-ABS blends, and polycarbonate-ABS blends, in which theamount of ABS may typically vary from about 1 to about 45 wt. %. Anespecially preferred phosphoramide isN,N′-bis-[di-(2,6-xylyl)-phosphoryl]-piperazine. It should also be clearthat the present invention includes compositions made by the methods aswell as articles made from the compositions.

Preparation methods for the compositions of the invention are typical ofthose employed for resinous blends. They may include such steps as dryblending followed by melt processing, the latter operation frequentlybeing performed under continuous conditions as by extrusion. Followingmelt processing, the compositions are molded into test specimens byconventional means such as injection molding.

The addition of at least one phosphoramide and at least one adjunctflame retardant to the compositions of the present invention may be bymixing all of the blend components together prior to melt processing.Alternatively, either one of, or both of at least one phosphoramide andat least one adjunct flame retardant may be combined with at least oneresinous blend component as a concentrate in a prior processing step.Such concentrates are often made by melt processing. The concentrate maythen be combined with the remaining blend components.

The various embodiments of the invention are inclusive of simple blendscomprising at least one thermoplastic resin and at least onephosphoramide and at least one adjunct flame retardant, and also ofcompositions in which one or more of said materials has undergonechemical reaction, either by itself or in combination with another blendcomponent. When proportions are specified, they apply to the originallyincorporated materials rather than those remaining after any suchreaction.

In another of its embodiments the present invention comprises articlesof manufacture made from the instantly disclosed compositions. Sucharticles may be transparent, translucent, or opaque depending upon theblend composition. Said articles can be made by any convenient meansknown in the art. Typical means include, but are not limited to,injection molding, thermoforming, blow molding, and calendering.Especially preferred articles include indirect and direct wounddeflection yokes for all cathode ray tube applications includingtelevision and computer monitors, slit type deflection yokes, mold coildeflection yokes, television backplates, docking stations, pedestals,bezels, pallets, electronic equipment such as switches, switch housings,plugs, plug housings, electrical connectors, connecting devices,sockets; housings for electronic equipment such as television cabinets,computer housings, including desk-top computers, portable computers,lap-top computers, palm-held computers; monitor housings, printerhousings, keyboards, FAX machine housings, copier housings, telephonehousings, mobile phone housings, radio sender and/or receiver housings,lights and lighting fixtures, battery chargers, battery housings,antenna housings, transformers, modems, cartridges, network interfacedevices, circuit breakers, meter housings, panels for wet and dryappliances such as dishwashers, clothes washers, clothes dryers,refrigerators; heating and ventilation enclosures, fans, air conditionerhousings, cladding and seating for indoor and outdoor application suchas public transportation including trains, subways, buses; automotiveelectrical components; articles used in glazing applications, such asroofs, greenhouses, sunrooms, swimming pool enclosures, windows.

The invention is illustrated by the following examples. All parts andpercentages are by weight. Intrinsic viscosity was determined inchloroform at 25° C. HDT values were determined at 264 psi (1820 kPa)according to ASTM procedure D648.

EXAMPLE 1

Blends of various amounts of a bisphenol A homopolycarbonate, 6.5 partsof a commercially available high rubber graft ABS copolymer and 9 partsof a commercially available SAN copolymer were prepared under identicalconditions by blending in a Henschel mixer followed by extrusion on atwin screw extruder and were molded into test specimens. The blends alsocontained conventional additives including 0.4 part ofpolytetrafluoroethylene dispersed within styrene-acrylonitrile copolymeras an anti-drip agent, which were not considered in determiningproportions, and various amounts of the following phosphoryl-based flameretardant additives:

N,N′-bis-[di-(2,6-xylyl)phosphoryl]piperazine (XPP), a compoundaccording to formula VI:

wherein each A moiety is a 2,6-dimethylphenoxy residue;N,N′-bis(neopentylenedioxy phosphoryl)piperazine (NPP), a compound ofsimilar structure but wherein each pair of A moieties on each phosphorusatom (e.g. the A³ and A⁴ pair) is a bridging neopentyloxy residue;N,N′-bis(diphenyl phosphoryl)piperazine (PPP), a compound of similarstructure but wherein each A moiety is a phenoxy residue; and resorcinolbis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate)(BPADP), two conventional phosphate esters. The FOT (total flameouttimes for first and second ignitions for 5 bars of 0.125 inch thickness)and Tg of the polycarbonate phase of each test specimen was determinedand the results are given in Table I.

TABLE I Sample Base 1 2 3 4 5 Polycarbonate, 81.3 72.2 76.9 73.9 73.671.6 parts FR, identity none XPP NPP PPP RDP BPADP FR, phr 0 12.4 6.910.4 10.7 13.2 FR, phr P 0 1.16 1.11 0.97 1.02 FR, % P 0 1.02 1.01 1.041.03 1.04 FOT, sec burns 19.4 84 — 20.3 27.3 Tg, ° C. 147 131 149 121111 112

It is apparent that the compositions of this invention had ansignificantly reduced FOT and a Tg that differed from that ofpolycarbonate (147° C.) in a base composition not containing aphosphoramide or phosphate ester by an acceptable increment. Sample 2had a Tg essentially equal within experimental error to that of thepolycarbonate in the base composition but the FOT was appreciably higherthan that obtained with XPP. Sample 3 utilizing PPP had a significantlylower Tg that that of XPP and NPP, yet exhibited similar FOT as obtainedwith XPP. It was unexpected that XPP-containing compositions (e.g.,sample 1) would exhibit such superior FOT as compared to NPP-containingcompositions (e.g., sample 2), and such a large increase inpolycarbonate Tg as compared to PPP-containing compositions (e.g.,sample 3). Samples 4 and 5, employing conventional flame retardants(FR), had unacceptably low Tg's for many commercial applications. Thevariations in FR content in terms of phr of total FR and of phosphorusare not considered significant from the standpoint of properties.

EXAMPLE 2

In the same base composition used for Example 1, a composition was madecontaining 4.5 parts RDP and 5.7 XPP. The resultant composition has aflame out time of 17 seconds and the polycarbonate had a Tg of 127° C.The glass transition temperature is higher for this composition thatwould be expected based upon the results obtained in samples 1 and 4.

EXAMPLE 3

Blends of 62 parts of a commercially availablepoly(2,6-dimethyl-1,4-phenylene ether) and 38 parts of a commerciallyavailable HIPS were prepared and molded under identical conditionssimilar to those of Example 1. The blends also contained conventionaladditives including 0.21 part of apolytetrafluoroethylene/styrene-acrylonitrile copolymer as an anti-dripagent, which were not considered in determining proportions, and 20.5phr of XPP, RDP and BPADP as phosphoryl-based flame retardant additives.The FOT (total flameout times for first and second ignitions for 5 barsof 0.06 inch thickness) and heat deflection temperature (HDT) of eachtest specimen was determined and the results are given in Table II.

TABLE II Sample 6 7 8 FR, identity XPP RDP BPADP FR, phr P 1.92 1.851.58 FOT, sec 24 21 37 HDT, ° C. 223.9 177.9 190.5

Again, it is apparent that the composition of the invention (Sample 6)had acceptable FR properties and a significantly higher HDT than thecompositions containing conventional FR additives, indicating superiorhigh temperature properties.

EXAMPLE 4

A blend of 40 parts of a commercially availablepoly(2,6-dimethyl-1,4-phenylene ether) and 60 parts of a commerciallyavailable HIPS were prepared and molded under conditions similar tothose of Example 3, using N,N′-bis[di-(2,6-xylyl)phosphoryl]piperazine(XPP) as the flame retardant material in essentially the sameproportion. The observed FOT was 34 seconds.

EXAMPLE 5

A commercially available HIPS, optionally containingpoly(2,6-dimethyl-1,4-phenylene ether) and/or apolystyrene-polybutadiene-polystyrene elastomer, were prepared andmolded under conditions similar to those of Example 1, usingN,N′-bis[di-(2,6-xylyl)phosphoryl]piperazine (XPP) as the flameretardant material. The compositions and flame out times (FOT, asdefined above for Table 1) are provided in Table III.

TABLE III Sample Base 9 10 11 12 13 HIPS, parts 100 90 70 65 72 78.5PPE, parts 0 0 0 25 7 3.5 Rubber, parts 0 0 0 0 2 3.5 XPP, parts 0 10 3010 19 14 FOT, sec burns 320 135 400 215 315 HDT, ° C., 264 psi 86 74 6879 71 73

As seen by the above data, phosphoramides as described herein areeffective in reducing the flame out time of HIPS, optionally in thepresence of PPE and/or rubber. It was unexpected that the flame outtimes would be so dramatically improved, i.e. decreased, with theaddition of the phosphoramide to render the material V-2 under UL-94classification. It was also unexpected that the HDT would be so high forthe compositions containing the phosphoramide.

EXAMPLE 6

Blends of 90 parts of a commercially available bisphenol A polycarbonatewere prepared containing 10 parts of either RDP or XPP. The blends alsocontained conventional additives, including a UV screener and anantioxidant, which were not considered in determining proportions. Thecompositions were extruded and molded into transparent specimens.Optical properties (according to ASTM 1003-61), including %transmission, yellowness index, and haze, and the Tg of thepolycarbonate phase were determined for test specimens of each blend.The results are given in Table IV along with results for a comparablecomposition containing essentially 100% of the same polycarbonate and noadded flame retardant.

TABLE IV Sample Base 14 15 Polycarbonate 100 90 90 RDP 0 10 0 XPP 0 0 10Tg, ° C. 149 111 131 Transmission, % 90.1 88.3 89.5 Haze 0.7 3.3 0.7Yellowness index 2.24 3.18 4.16

The above data show that the composition containing XPP has the same %transmission and haze as a specimen of essentially pure polycarbonate,and an acceptable yellowness index. Compared to the base sample, thedecrease in polycarbonate Tg is only 18° C. for the specimen containingXPP compared to 38° C. for the specimen containing RDP.

EXAMPLE 7

A blend of 26.5 parts of a first bisphenol A homopolycarbonate, 61.8parts of a second bisphenol A homopolycarbonate with weight averagemolecular weight about 71% of that of the first bisphenol Ahomopolycarbonate, 4 parts of a commercially available bulk ABScopolymer, and 5 parts XPP was prepared by blending in a Henschel mixerfollowed by extrusion on a twin screw extruder and molded into testspecimens. The blend also contained 2.75 parts conventional additivesincluding titanium dioxide and polytetrafluoro-ethylene dispersed withinstyrene-acrylonitrile copolymer as an anti-drip agent. Measurement ofthe Melt Volume Rate (260° C. and 5 kilograms applied weight) for theblend gave a value of 24.9 cubic centimeters per 10 minutes. The blendshowed a melt viscosity at 280° C. of 390 Pascal-seconds (Pa-s) at ashear rate of 100 sec⁻¹, 220 Pa-s at a shear rate of 1500 sec⁻¹, and 72Pa-s at a shear rate of 10000 sec⁻¹. The observed FOT (total flameouttimes for first and second ignitions for 5 bars of 0.06 inch thickness)was 21.5 seconds. A Ball Pressure Test run on test specimens at 125° C.according to test protocol IEC 695-10-2 (1995-08) gave puncture diameterof 1.6 millimeters (mm). Typically, a value of less than 2 mm isdesirable for most applications.

EXAMPLE 8

A blend of 64.3 parts bisphenol A homopolycarbonate, 16 parts of acopolycarbonate comprising 45 mole % bisphenol A and 55 mole %4,4′-(3,3,5-trimethylcyclohexylidene)diphenol (APEC 9371 obtained fromBayer Corp.); 4 parts of a commercially available high rubber graft ABScopolymer; 6 parts of a commercially available SAN copolymer, and 9parts XPP was prepared by blending in a Henschel mixer followed byextrusion on a twin screw extruder and molded into test specimens. Theblend also contained 0.7 parts of conventional additives includingpolytetrafluoroethylene dispersed within styrene-acrylonitrile copolymeras an anti-drip agent. The blend showed a glass transition temperatureof 139° C. The observed FOT (total flameout times for first and secondignitions for 5 bars of 0.06 inch thickness) was 24 seconds.

EXAMPLE 9

The same composition of Example 8 was prepared except that 16 parts of acopolycarbonate comprising 65 mole % bisphenol A and 35 mole %4,4′-(3,3,5-trimethylcyclo-hexylidene)diphenol (APEC 9351 obtained fromBayer Corp.) was used. The blend showed a glass transition temperatureof 140° C. The observed FOT (total flameout times for first and secondignitions for 5 bars of 0.06 inch thickness) was 21 seconds.

EXAMPLE 10

A blend of 58.8 parts bisphenol A homopolycarbonate, 25 parts of acopolycarbonate comprising 65 mole % bisphenol A and 35 mole %4,4′-(3,3,5-trimethylcyclohexylidene)diphenol (APEC 9351 obtained fromBayer Corp.); 4 parts of a commercially available high rubber graft ABScopolymer; 2 parts of a commercially available SAN copolymer, 0.5 partsCLAYTONE HY, and 9 parts XPP was prepared by blending in a Henschelmixer followed by extrusion on a twin screw extruder and molded intotest specimens. The blend also contained 0.7 parts of conventionaladditives including polytetrafluoroethylene dispersed withinstyrene-acrylonitrile copolymer as an anti-drip agent. The blend showeda glass transition temperature of 140° C. The observed FOT (totalflameout times for first and second ignitions for 5 bars of 0.06 inchthickness) was 19 seconds.

EXAMPLES 11-25

Blends of 88 parts of a commercially available bisphenol Ahomopolycarbonate, 6 parts of a commercially available high rubber graftABS copolymer and 4.5 parts of a commercially available SAN copolymerwere prepared under conditions similar to those used for Example 1. Theblends also contained conventional additives, including 0.5 part ofpolytetrafluoroethylene dispersed within styrene-acrylonitrile copolymeras an anti-drip agent, which were not considered in determiningproportions. The blends also contained various amounts (in phr) of XPPand adjunct flame retardants. The compositions, flame out times (FOT, asdefined above for Table I), and UL-94 ratings are provided in Table V.

TABLE V Material, phr 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 XPP10.4 8.1 8.1 8.2 8.3 8.1 8.1 8.2 8.1 8.1 8.1 8.1 8.2 8.3 8.5 antimony 00 0.5 1.1 2.2 0 0 0 0 0 0 0 0 0 0 oxide boron 0 0 0 0 0 0.27 0.55 1.1 00 0 0 0 0 0 phosphate Organoclay 0 0 0 0 0 0 0 0 0.27 0.55 0 0 0 0 0 HYOrganoclay 0 0 0 0 0 0 0 0 0 0 0.27 0.55 0 0 0 APA PPS* 0 0 0 0 0 0 0 00 0 0 0 1.1 2.2 4.6 FOT, sec. 30 70 20 4 109 30 42 35 7 35 15 27 24 5367 UL 94 rating V-0 V-1 V-0 V-0 V-2 V-0 V-1 V-1 V-0 V-1 V-0 V-1 V-0 V-1V-1 *PPS = polyphenylene sulfide

Samples 11 and 12 are control sample containing two different amounts ofXPP and no adjunct flame retardant. It can be seen that the UL-94 ratingchanges from V-0 to V-1 when a lower amount of XPP is used in controlsample 12. The samples containing adjunct flame retardant demonstratethat compositions with acceptable UL-94 ratings can be made by themethod of the invention. Compositions containing certain amounts ofadjunct flame retardant have UL-94 rating that is as good as the ratingfor the control sample 11 although they contain only as much XPP ascontrol sample 12.

EXAMPLES 26-32

Blends of 25 parts of a bisphenol A polycarbonate with weight averagemolecular weight about 30,000 and 75 parts of a bisphenol Apolycarbonate with lower weight average molecular weight were prepared.The blends contained various amounts of XPP, and of potassiumdiphenylsulfone-3-sulfonate (referred to as “KSS”) as adjunct flameretardant. The blends also contained conventional additives which werenot considered in determining proportions. The compositions wereextruded and molded into transparent specimens. The total flame outtimes for first and second ignitions for 5 bars of each sample weredetermined using bars of both of 0.060 inch thickness and of 0.125 inchthickness. Optical properties, including yellowness index (according toASTM D1925) and haze (according to ASTM 1003), were determined for testspecimens of each blend. The results are given in Table VI along withresults for a control composition (sample 24) containing the samepolycarbonate mixture and a commercially available brominatedpolycarbonate flame retardant (PC-B).

TABLE VI Material, phr 26 27 28 29 30 31 32 PC-B 0.5 0 0 0 0 0 0 KSS0.25 0.15 0.05 0.05 0.25 0.05 0.15 XPP 0 0.5 0.1 0.9 0.9 0.1 0.5 FOT-a,sec. 19 26 36 64 61 25 35 FOT-b, sec. 24 34 56 83 31 48 53 Yellowness 22.5 2.3 2.8 3.4 1.8 2 Index Haze 1 0.6 0.7 0.5 1 0.5 0.5

FOT-a=measured on 0.125 inch thickness test bars

FOT-b=measured on 0.060 inch thickness test bars

The data show that samples with acceptable FOT values can be made by themethod of the invention. Samples containing XPP and adjunct flameretardant demonstrate optical properties comparable to those for asimilar blend containing only a commercially available brominated flameretardant.

EXAMPLES 33-41

Blends of a commercially available bisphenol A homopolycarbonate, acommercially available high rubber graft ABS copolymer and acommercially available SAN copolymer were prepared under conditionssimilar to those used for Example 1. The blends also contained 0.7 partof conventional additives, including polytetrafluoroethylene dispersedwithin styrene-acrylonitrile copolymer as an anti-drip agent, which werenot considered in determining proportions. The blends also containedvarious amounts (in phr) of XPP, CLAYTONE HY, and a commerciallyavailable polyphenylsulfone (RADEL R available from Amoco Chemical Co.).As adjunct flame retardants. The compositions, flame out times (FOT, asdefined above for Table I), UL-94 ratings, and Limiting Oxygen Indicesare provided in Table VII.

TABLE VII Material 33 34 35 36 37 38 39 40 41 PC 77.8 70.3 77.8 73.865.8 73.8 77.8 77.8 79.3 ABS 4 8 4 4 8 4 4 8 7 SAN 6 2 2 6 6 6 2 6 2 XPP9 9 5 5.5 9 5.5 5 5 9 Organoclay HY 0.5 0 0.5 0 0.5 0 0.5 0.5 0 PPSO* 210 10 10 10 10 10 2 2 FOT, sec. 14 30 30 70 53 52 43 240 24 UL 94 ratingV-0 V-0 V-0 V-1 V-1 V-1 V-1 — V-0 LOI 34 — 35.9 — — — — 30 —*polyphenylsulfone

EXAMPLES 42-54 Comparative Examples C42-C48

Blends of 72.19 parts of a bisphenol A polycarbonate with weight averagemolecular weight about 30,000 and between about 22 and about 28 parts ofa bisphenol A polycarbonate (PC-2) with higher weight average molecularweight were prepared by extrusion and molded into test parts. The blendscontained various amounts of XPP, and of RDP as adjunct flame retardant.The RDP was added in the form of a masterbatch in polycarbonatecontaining 25 wt. % RDP. The blends also contained less than 0.3 wt. %conventional additives which were not considered in determiningproportions. Blends of this type are particularly useful for forminginto transparent sheet and articles made therefrom. Samples were testedfor melt volume rate (MVR according to ISO 1133 in units of cubiccentimeters per 10 minutes) at 300° C. and 1.2 kg. load, and for UL94flame resistance at 3.2 mm. thickness, and for percentage pass in flametest NF-P-92-505 at 3.2 mm. thickness. This test method is NormeFrancaise NF-P-92-505 of L'Association Francaise de Normalisation(AFNOR), Paris, France, which is hereby incorporated by reference. Inthis test, a test sample, having dimensions of 7 cm.×7 cm. and having aminimum weight of 2 grams, is placed on a support grid located thirtymillimeters (mm) under a radiator. A drop receptacle containing cottonwool is placed three-hundred mm below the support grid. The radiator isa horizontal 500 Watt electric radiator which irradiates the sample witha radiation intensity of three Watts per square centimeter. The testlasts for a total of ten minutes. If the specimen ignites within thefirst five minutes after turning on the radiator, the radiator isremoved three seconds after ignition and radiation is continued as soonas the specimen extinguishes. During the second five minutes, radiationis maintained regardless of whether the sample burns. During the test,the radiator is operated for ten minutes. A sample fails this test ifthe cotton wool starts to burn. Table VIII shows test results for theseblends. Samples 45 and 52 were similar in composition.

TABLE VIII Material 42 43 44 45 46 47 48 49 50 51 52 PC-2 27.81 26.0326.13 24.46 22.99 24.36 24.56 25.93 22.89 22.79 24.46 XPP 0 0.2 0.1 0.20.1 0.3 0.1 0.3 0.2 0.3 0.2 RDP/PC masterbatch 0 1.57 1.57 3.14 4.713.14 3.14 1.57 4.71 4.71 3.14 MVR (cc/10 min.) 6.74 5.42 4.97 5.35 5.465.67 5.08 5.12 5.74 5.63 5.39 UL 94 rating V-2 V-2 V-2 V-2 V-2 V-2 V-2V-2 V-2 V-2 V-2 test NF-P-92-505* 30 70 70 80 60 60 70 40 90 40 70 %pass *10 plaques tested

The addition of XPP in combination with RDP gives no improvement in UL94test results over a similar formulation without these additives but,surprisingly, there is obtained an increased pass rate in flamabilitytest NF-P-92-505.

For comparison purposes similar blends of the two polycarbonatescontaining various levels of both KSS and PC-B were prepared byextrusion and molded into test parts; these blends also contained lessthan 0.3 wt. % conventional additives which were not considered indetermining proportions. Samples were tested as described above. TableIX shows test results for these comparative examples. Samples C43 andC48 were similar in composition.

TABLE IX Material C42 C43 C44 C45 C46 C47 C48 PC-2 27.81 26.75 27.2726.27 27.23 26.23 26.75 PC-B 0 1.0 0.5 1.5 0.5 1.5 1.0 KSS 0 0.05 0.030.03 0.07 0.07 0.05 MVR (cc/10 min.) 4.6 4.6 4.7 4.8 4.7 4.6 4.5 UL 94rating V-2 V-0 V-0 V-0 V-0 V-0 V-0 test NF-P-92-505*, 22 11 33 22 33 0 0% pass *9 plaques tested

The addition of PC-B in combination with KSS gives an improvement inUL94 test results over a similar formulation without these additives butthe improved UL94 performance does not result in an increased pass ratein the dripping test.

EXAMPLE 55

Bisphosphoramidates were prepared by the reaction of piperazine with amixed diaryl chlorophosphate of the formula (ArO)(Ar′O)POCl in thepresence of a tertiary amine as described in Talley, J. Chem. Eng. Data,33, 221-222 (1988), the disclosure of which is incorporated by referenceherein. Table X shows the compositions of the phosphoramidates and theircorresponding glass transition points and melting points.

TABLE X Phenol or phenol mixture Composition Tg, ° C. Tm, ° C.2,6-xylenol 100 62 192 2,4,6-trimethylphenol 100 74 234-236 phenol 100 0188-190 2,6-xylenol/ 90/10 62 183-187 2,4,6-trimethylphenol 2,6-xylenol/75/25 65 187-194 2,4,6-trimethylphenol 2,6-xylenol/ 90/10 59 179-194phenol

EXAMPLE 56

Blends with compositions as in Example 1 containing about 71-77 parts ofa bisphenol A homopolycarbonate, 6.5 parts of a commercially availablehigh rubber graft ABS copolymer and 9 parts of a commercially availableSAN copolymer are prepared under identical conditions by blending in aHenschel mixer followed by extrusion on a twin screw extruder and aremolded into test specimens. The blends contain various amounts ofphosphorus-containing flame retardants such that the total amount ofphosphorus by weight in the composition is between about 1.01% and1.04%. The blends also contain conventional additives including 0.4 partof polytetrafluoroethylene dispersed within styrene-acrylonitrilecopolymer as an anti-drip agent. The following phosphoryl-based flameretardant additives are employed: a mixed aryloxy compound according toformula VI:

wherein the A moiety is derived from a 90/10 mixture of2,6-xylenol/phenol residues (hereinafter referred to as mixed aryloxycompound); N,N′-bis(neopentylenedioxy phosphoryl)piperazine (NPP), acompound of similar structure but wherein each pair of A moieties oneach phosphorus atom (e.g. the A³ and A⁴ pair) is a bridgingneopentyloxy residue; N,N′-bis(diphenyl phosphoryl)piperazine (PPP), acompound of similar structure but wherein each A moiety is a phenoxyresidue; and resorcinol bis(diphenyl phosphate) (RDP) and bisphenol Abis(diphenyl phosphate) (BPADP), two conventional phosphate esters. TheFOT (total flameout times for first and second ignitions for 5 bars of0.125 inch thickness) and Tg of the polycarbonate phase of each testspecimen are determined. The compositions containing the mixed aryloxycompound have an significantly reduced FOT and a Tg that differs by anacceptable increment from that of polycarbonate (147° C.) in a basecomposition as in Example 1 not containing a phosphoramide or phosphateester. The composition containing the mixed aryloxy compound exhibitssuperior FOT as compared to the NPP-containing composition and shows alarge increase in polycarbonate Tg as compared to the PPP-containingcomposition. The samples employing conventional flame retardants (FR)have lower Tg's than the corresponding Tg for the sample containing themixed aryloxy compound. The variations in FR content in terms of phr oftotal FR and of phosphorus are not considered significant from thestandpoint of properties.

EXAMPLE 57

In the same base composition used for Example 1, a composition was madecontaining 4.5 parts RDP and 5.7 of the mixed aryloxy compound ofExample 56. The resultant composition has an acceptable flame out time.The glass transition temperature is higher for this composition that forthe corresponding composition containing an amount of RDP alone withcomparable level of total phosphorus by weight.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions and examples should not bedeemed to be a limitation on the scope of the invention. Accordingly,various modifications, adaptations, and alternatives may occur to oneskilled in the art without departing from the spirit and scope of thepresent invention.

What is claimed is:
 1. A resin composition comprising the following andany reaction products thereof: a) at least one thermoplastic resin, andb) at least one phosphoramide having a glass transition point of atleast about 0° C. of the formula:

wherein each Q¹ is independently oxygen or sulfur; and each of A³⁻⁶ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue; and c) at leastone adjunct flame retardant compound.
 2. The composition of claim 1wherein at least one phosphoramide has a glass transition point of atleast about 10° C.
 3. The composition of claim 1 wherein all of thephosphoramide of component b) has a glass transition point of at leastabout 10° C.
 4. The composition of claim 1 wherein at least onephosphoramide has a glass transition point of at least about 20° C. 5.The composition of claim 1 wherein all of the phosphoramide of componentb) has a glass transition point of at least about 20° C.
 6. Thecomposition of claim 1 wherein each Q¹ is oxygen; and each of A³⁻⁶ is anaryloxy moiety with at least one aryloxy moiety having at least onesubstituent on an aromatic ring ortho to the oxygen linkage.
 7. Thecomposition of claim 6 wherein each substituent is a C₁₋₈ straight-chainor branched alkyl, or halogen.
 8. The composition of claim 1 whereineach Q¹ is oxygen; and each of A³⁻⁶ is independently an aryloxy moietywith at least one substituent on each aromatic ring ortho to the oxygenlinkage.
 9. The composition of claim 8 wherein each substituent is aC₁₋₈ straight-chain or branched alkyl, or halogen.
 10. The compositionof claim 1 wherein each Q¹ is oxygen; and each of A³⁻⁶ is independentlyan aryloxy moiety with at least two substituents on each aromatic ringortho to the oxygen linkage.
 11. The composition of claim 10 whereineach substituent is a C₁₋₈ straight-chain or branched alkyl, or halogen.12. The composition of claim 1 wherein each Q¹ is oxygen; and each ofA³⁻⁶ is independently phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,2,3,6-trimethylphenoxy, or 2,4,6-trimethylphenoxy.
 13. The compositionof claim 1 wherein the at least one thermoplastic resin is selected fromthe group consisting of (i) polycarbonate resins and blends containingat least one polycarbonate resin, (ii) polyphenylene ether resins andblends containing at least one polyphenylene ether resin, (iii)polystyrene resin and blends containing polystyrene resin, (iv)styrene-containing copolymer resin and blends containingstyrene-containing copolymer resin; (v) styrene-containing graftcopolymer resin and blends containing styrene-containing graft copolymerresin; and (vi) high impact polystyrene resin and blends containing highimpact polystyrene resin.
 14. The composition of claim 1 wherein the atleast one thermoplastic resin is selected from the group consisting ofhigh impact polystyrene resin, syndiotactic polystyrene, polyphenyleneether/high impact polystyrene resin blends, polyphenyleneether/syndiotactic polystyrene resin blends, polycarbonate-SAN blends,polycarbonate-ABS blends, polycarbonate-SAN-ABS blends, andpolycarbonate-polyester blends.
 15. The composition of claim 1 whereinthe thermoplastic resin is at least one of polycarbonates, polyphenyleneethers, high impact polystyrenes, syndiotactic polystyrenes,acrylonitrile-butadiene-styrene copolymers, and styrene-acrylonitrilecopolymers.
 16. The composition of claim 1 wherein the thermoplasticresin comprises at least one polycarbonate resin.
 17. The composition ofclaim 16 further comprising at least one ABS resin.
 18. The compositionof claim 16 wherein the at least one polycarbonate comprises bisphenol Apolycarbonate and a copolycarbonate of bisphenol A and4,4′-(3,3,5-trimethylcyclohexylidene)diphenol.
 19. The composition ofclaim 16 wherein the at least one polycarbonate comprises at least twomolecular weight grades of bisphenol A polycarbonate.
 20. Thecomposition of claim 16 wherein the at least one phosphoramide comprisesa phosphoramide of the formula VI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is independently phenoxy,2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or2,4,6-trimethylphenoxy.
 21. The composition of claim 16 wherein the atleast one phosphoramide comprises a phosphoramide of the formula VI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is 2,6-dimethylphenoxy. 22.The composition of claim 1 wherein the at least one thermoplastic resincomprises poly(2,6-dimethyl-1,4-phenylene ether).
 23. The composition ofclaim 22 wherein the at least one phosphoramide comprises aphosphoramide of the formula VI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is independently phenoxy,2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or2,4,6-trimethylphenoxy.
 24. The composition of claim 23 wherein the atleast one phosphoramide comprises a phosphoramide of the formula VI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is 2,6-dimethylphenoxy. 25.The composition of claim 1 wherein the adjunct flame retardant comprisesat least one polymeric or non-polymeric member selected from the groupconsisting of phosphate esters, thiophosphate esters, phosphonateesters, thiophosphonate esters, phosphinate esters, thiophosphinateesters, phosphines, phosphine oxides, thiophosphine oxides, phosphoniumsalts; phosphate salts, thiophosphate salts, phosphonate salts,thiophosphonate salts, phosphinate salts, thiophosphinate salts,pyrophosphate salts, metaphosphate salts; sulfonate salts, sulfinatesalts, sulfones, sulfoxides, sulfides; borates; antimony salts;siloxanes; and organoclays.
 26. The composition of claim 25 wherein theadjunct flame retardant comprises at least one polymeric ornon-polymeric member selected from the group consisting of phosphateesters, phosphate salts, sulfonate salts, sulfones, sulfides, borates,antimony salts; siloxanes; and organoclays.
 27. The composition of claim26 wherein the adjunct flame retardant comprises at least one memberselected from the group consisting of resorcinol bis(diphenylphosphate),bisphenol A bis(diphenylphosphate), triphenylphosphate,tricresylphosphate, boron phosphate, potassiumdiphenylsulfone-3-sulfonate, potassium perfluorobutane sulfonate,polyphenylene sulfide, polyphenylsulfone, zinc borate, antimony oxide;polysiloxanes; and organoclays.
 28. The composition of claim 27 whereinthe at least one phosphoramide comprises a phosphoramide of the formulaVI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is independently phenoxy,2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy, or2,4,6-trimethylphenoxy.
 29. The composition of claim 28 wherein thecombination of the at least one phosphoramide and the at least oneadjunct flame retardant is present in an amount effective to render theresin composition a flame rating of V-0, V-1, or V-2 in theUnderwriter's Laboratory UL-94 protocol when measured on a test specimenof about 0.125 inch by about 0.5 inch by about 5 inch dimensions. 30.The composition of claim 28 wherein the combination of the at least onephosphoramide and the at least one adjunct flame retardant is present inan amount effective to provide at least a 50% pass rate in ten testspecimens in the Norme Francaise NF-P-92-505 flammability test ofL'Association Francaise de Normalisation using test specimens withdensity between about 1.2 to about 6.0 kilograms per square meter. 31.The composition of claim 30 wherein the phosphoramide comprises aphosphoramide of the formula VI:

wherein each Q¹ is oxygen; and each of A³⁻⁶ is 2,6-dimethylphenoxy, andthe adjunct flame retardant is resorcinol diphosphate.
 32. Thecomposition of claim 1 wherein at least one phosphoramide is present inan amount effective to render the resin composition a flame rating ofV-0, V-1, or V-2 in the Underwriter's Laboratory UL-94 protocol whenmeasured on a test specimen of about 0.125 inch by about 0.5 inch byabout 5 inch dimensions.
 33. The composition of claim 1 wherein thetotal amount of phosphorus per 100 parts of resinous materials is in therange of about 0.008-3 parts by weight.
 34. The composition of claim 29wherein the total amount of phosphorus per 100 parts of resinousmaterials is in the range of about 0.008-3 parts by weight.
 35. Thecomposition of claim 30 wherein the total amount of phosphorus per 100parts of resinous materials is in the range of about 0.008-3 parts byweight.
 36. The composition of claim 35 wherein the total amount ofphosphorus per 100 parts of resinous materials is in the range of about0.05-0.2 parts by weight.
 37. The composition of claim 1 which isessentially free of chlorine and bromine.
 38. An article made from thecomposition of claim
 1. 39. The article of claim 38 which is adeflection yoke for cathode ray tube, deflection yoke for television,slit type deflection yoke, mold coil deflection yoke, televisionbackplate, docking station, pedestal, bezel, pallet, switch, switchhousing, plug, plug housing, electrical connector, connecting device,socket, television housing, computer housing, desk-top computer housing,portable computer housing, lap-top computer housing, palm-held computerhousing; monitor housing, printer housing, keyboard, FAX machinehousing, copier housing, telephone housing, mobile phone housing, radiosender housing, radio receiver housing, light fixture, battery chargerhousing, battery housing, automotive electrical component, antennahousing, transformer housing, modem, cartridge, network interface devicehousing, circuit breaker housing, meter housing, panel for wet or dryappliance, dishwasher panel, clothes washer panel, clothes dryer panel,refrigerator panel; heating or ventilation enclosure, fan, airconditioner housing, cladding or seating for public transportation; orcladding or seating for trains, subways, or buses; an article used in aglazing application, a roof, greenhouse, sunroom, swimming poolenclosure, or window.
 40. A method to increase the heat distortiontemperature of a flame resistant composition containing an amount of atleast one phosphoramide and at least one adjunct flame retardanteffective to render the composition a flame rating of at least V-2 inthe Underwriter's Laboratory UL-94 protocol when measured on a testspecimen of about 0.125 inch by about 0.5 inch by about 5 inchdimensions, wherein the method comprises combining (a) at least onethermoplastic resin selected from the group consisting of (i)polycarbonate resins and blends containing at least one polycarbonateresin, (ii) polyphenylene ether resins and blends containing at leastone polyphenylene ether resin, (iii) polystyrene resin and blendscontaining polystyrene resin, (iv) styrene-containing copolymer resinand blends containing styrene-containing copolymer resin; (v)styrene-containing graft copolymer resin and blends containingstyrene-containing graft copolymer resin; and (vi) high impactpolystyrene resin and blends containing high impact polystyrene resin,and (b) at least one phosphoramide having a glass transition point of atleast about 0° C. of the formula VI:

wherein each Q¹ is independently oxygen or sulfur; and each of A³⁻⁶ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue; and c) at leastone polymeric or non-polymeric member selected from the group consistingof phosphate esters, thiophosphate esters, phosphonate esters,thiophosphonate esters, phosphinate esters, thiophosphinate esters,phosphines, phosphine oxides, thiophosphine oxides, phosphonium salts;phosphate salts, thiophosphate salts, phosphonate salts, thiophosphonatesalts, phosphinate salts, thiophosphinate salts, pyrophosphate salts,metaphosphate salts; sulfonate salts, sulfinate salts, sulfones,sulfoxides, sulfides; borates; antimony salts; siloxanes; andorganoclays.
 41. The method of claim 40 wherein the composition has aflame rating of least V-1.
 42. The method of claim 40 wherein thecomposition has a flame rating of least V-0.
 43. The method of claim 40wherein at least one phosphoramide has a glass transition point of atleast about 10° C.
 44. The method of claim 40 wherein the phosphoramidehas a glass transition point of at least about 10° C.
 45. The method ofclaim 40 wherein at least one phosphoramide has a glass transition pointof at least about 20° C.
 46. The method of claim 40 wherein thephosphoramide has a glass transition point of at least about 20° C. 47.The method of claim 40 wherein each Q¹ is oxygen; and each of A³⁻⁶ is anaryloxy moiety with at least one aryloxy moiety having at least onesubstituent on an aromatic ring ortho to the oxygen linkage.
 48. Themethod of claim 47 wherein each substituent is a C₁₋₈ straight-chain orbranched alkyl, or halogen.
 49. The method of claim 40 wherein each Q¹is oxygen; and each of A³⁻⁶ is independently an aryloxy moiety with atleast one substituent on the aromatic ring ortho to the oxygen linkage.50. The method of claim 49 wherein each substituent is a C₁₋₈straight-chain or branched alkyl, or halogen.
 51. The method of claim 40wherein each Q¹ is oxygen; and each of A³⁻⁶ is independently an aryloxymoiety with at least two substituents on the aromatic ring ortho to theoxygen linkage.
 52. The method of claim 51 wherein each substituent is aC₁₋₈ straight-chain or branched alkyl, or halogen.
 53. The method ofclaim 40 wherein each Q¹ is oxygen; and each of A³⁻⁶ is independentlyphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,3,6-trimethylphenoxy,or 2,4,6-trimethylphenoxy.
 54. The method of claim 40 wherein thethermoplastic resin comprises at least one polycarbonate resin.
 55. Themethod of claim 54 wherein the composition further comprises at leastone ABS resin.
 56. The method of claim 54 wherein the at least onepolycarbonate comprises bisphenol A polycarbonate and a copolycarbonateof bisphenol A and 4,4′-(3,3,5-trimethylcyclohexylidene)diphenol. 57.The method of claim 40 wherein the adjunct flame retardant comprises atleast one polymeric or non-polymeric member selected from the groupconsisting of phosphate esters, phosphate salts, sulfonate salts,sulfides, sulfones, borates, antimony salts; siloxanes; and organoclays.58. The method of claim 57 wherein the adjunct flame retardant comprisesat least one member selected from the group consisting of resorcinolbis(diphenylphosphate), bisphenol A bis(diphenylphosphate),triphenylphosphate, tricresylphosphate, boron phosphate, potassiumdiphenylsulfone-3-sulfonate, potassium perfluorobutane sulfonate,polyphenylene sulfide, polyphenylsulfone, zinc borate, antimony oxide;polysiloxanes; and organoclays.
 59. The method of claim 40 in which thecomposition is essentially free of chlorine and bromine.
 60. The flameresistant composition made by the method of claim
 40. 61. The flameresistant composition made by the method of claim
 59. 62. A method toimprove the pass rate in the Norme Francaise NF-P-92-505 flammabilitytest of L'Association Francaise de Normalisation wherein the methodcomprises combining (a) at least one polycarbonate resin; (b) at leastone phosphoramide having a glass transition point of at least about 0°C. of the formula VI:

wherein each Q¹ is independently oxygen or sulfur; and each of A³⁻⁶ isindependently an alkyloxy, alkylthio, aryloxy, or arylthio residue, oran aryloxy or arylthio residue containing at least one alkyl or halogensubstitution, or mixture thereof; or an amine residue; and c) at leastone polymeric or non-polymeric member selected from the group consistingof phosphate esters, thiophosphate esters, phosphonate esters,thiophosphonate esters, phosphinate esters, thiophosphinate esters,phosphines, phosphine oxides, thiophosphine oxides, phosphonium salts;phosphate salts, thiophosphate salts, phosphonate salts, thiophosphonatesalts, phosphinate salts, thiophosphinate salts, pyrophosphate salts,metaphosphate salts; sulfonate salts, sulfinate salts, sulfones,sulfoxides, sulfides; borates; antimony salts; siloxanes; andorganoclays.